Bicyclic compounds and processes for making and using same

ABSTRACT

Bicyclic compounds containing four to six alkyl groups and having the formula:   WHEREIN THE DASHED LINE IS A SINGLE OR DOUBLE CARBON-TO-CARBON BOND; X is a carbonyl oxygen or two hydrogen atoms; Y is -CHR9or -CHR10-CHR11-; R1, R2, R3 and R4 are the same or different alkyl; R7, R8, R9, R10 and R11 are hydrogen or the same or different alkyl, R7 or R8 being alkyl when R9 is alkyl; R5 is not present and R6 is hydrogen when the dashed line is a double bond; and R5 and R6 are hydrogen, or taken together, form an oxirane ring when the dashed line is a single bond, together with methods of preparation for such bicyclic compounds, perfume compositions containing the compounds, and methods for altering aromas utilizing such compounds.

Hall et al.

[ Dec. 16, 1975 BICYCLIC COMPOUNDS AND PROCESSES FOR MAKING AND USINGSAME Inventors: John B. Hall, Rumson; Lekhu Kewalram Lala, Edison, bothof N.J-.; Muus G. J. Beets, l-lilversum, Netherlands; William I. Taylor,Summit, NJ.

Assignee: International Flavors & Fragrances Inc., New York, NY.

Filed: Nov. 1, 1973 Appl. No.: 411,789

Related US. Application Data Division of Ser. No. 263,219, June 15,1972,

abandoned.

us. or. 252/522; 260/348 c 1m. 01. A61K 7/46 Field of Search 252/522;260/348 c References Cited UNITED STATES PATENTS 10/1957 Stoll 252/52211/1959 Goldstein et al 252/522 1/1963 Saucy 252/522 8/1966 Blumenthal252/522 2/1974 l-lochstetler et al 260/348 C Primary Examiner-De1bert E.Gantz Assistant Examiner-Joseph A. Boska Attorney, Agent, or FirmBro0ksHaidt Haffner & Delahunty [57] ABSTRACT Bicyclic compounds containingfour to six alkyl groups and having the formula:

wherein the dashed line is a single or double carbonto-carbon bond; X isa carbonyl oxygen or two hydrogen atoms; Y is CHR or CHR -CHR R R R andR are the same or different alkyl; R R R R and R are hydrogen or thesame or different alkyl, R or R being alkyl when R, is alkyl; R is notpresent and R is hydrogen when the dashed line is a double bond; and Rand R are hydrogen, or taken together, form an oxirane ring when thedashed line is a single bond, together with methods of preparation forsuch bicyclic compounds, perfume compositions containing the compounds,and methods for altering aromas utilizing such compounds,

4 Claims, N0 Drawings BICYCLIC COMPOUNDS AND PROCESSES FOR MAKING ANDUSING SAME This is a division, of application Ser. No. 263,219, filedJune 15, 1972 now abandoned.

BACKGROUND OF THE INVENTION The present invention relates to polyalkylbicyclic compounds, together with preparation of such'compounds andtheir use for altering fragrances, and perfume compositions containingsuch bicyclic compounds.

There is a continuing need for fragrance materials having desirablewoody odors with satisfactory olfactory overtones or qualities. Manynatural products have such woody fragrances, but the more desirable ofthese are frequently in short supply, and hence difficult to obtain andexpensive. Further, while both natural and synthetic materials canprovide various woody fragrance qualities, many of these are fleetingand unsuitable for use in quality perfumes or other olfactorycompositions. Moreover, it is desirable to have such fragrance materialswith various overtones which canbe blended with other materials.

US. Pat. No. 3,265,739 shows a number of octalone materials which arestated to be useful for their fragrance propertiesfUS. Pat. No.3,636,165 shows by drogenated indanols as having useful fragrances, andUS. Pat. No. 3,647,826 shows epoxyperhydropentarnethylindane as having afine-pine-woody aroma. The use of perhydropentamethylindanone and oftetrahydropentamethylindane as fragrance compounds has also beensuggested.

A pentamethyldecahydronaphthalen-7-one material called Ketone BD-9 issued for its wood, amber fragrance properties. Belgian Pat. No. 763,168shows dialkyloctahydronaphthalenones and naphthalenols as perfumecompounds. Tetraalkylperhydroindanone has also been suggested as havinga musk, woody odor. Tetrahedron Letters 14, 627 shows indanonederivatives, as does Helvetica Chimica Acta 32(7), 2360. No aroma issuggested in these two journal articles, and similarly no odor issuggested for the naphthalenone derivatives shown in J.A.C.S. 85, 2014:

THE INVENTION The present invention provides novel compounds which aresuitable for a wide variety of perfume and other olfactory uses.Briefly, this invention contemplates bicyclic compounds containing atleast four alkyl substituents on the ring and the rings of whichcomprise a 6membered ring to which is fused either a S-membered ring, ora 6-membered hydrocarbon ring. The invention also contemplates the useof such novel compounds, the use thereof to provide variouspleasingaromas, perfume compositions containing the cornpounds; and variousarticles perfumed'therewith.

More particularly, the bicyclic compounds contain from four to six alkylgroups substituent on the ring and respond to the formula:

wherein the dashed line is a single or double carbon-tocarbon bond; X iscarbonyl oxygen or two hydrogen atoms; Y is CI-IR or Cl-IR -CI-IR, R R Rand R are the same or different alkyl; R R R R and R are hydrogen or thesame or different alkyl, R or R being alkyl when R is alkyl; R, is notpresent and R is hydrogen when the dashed-line is a double' bond; and; Rand R are hydrogen or, taken together, form an oxirane ring when thedashed line is a single bond. The polyalkyl substituents are desirablylower alkyl groups, preferably those having from one to three carbonatoms in the group. The alkyl groups can be the same or different, andin certain preferred embodiments of the invention they are all methyl.

Thus, the preferred polyalkyl bicyclic compounds include a4,5,6,7-tetrahydro-1,l,2,3,3,5-hexamethylinnaphthalene, a liquid havinga boiling point of 11 l-l 12C at 2.0 mm Hg and the formula:

perhydro-l l ,3,4,4,-hexamethylnaphthalene the formula:

1,2,3,4,5,6,7,8-octahydro-l,l,3 ,4,4-pentamethylnaphthalene, a liquidboiling at 8990C atllS mm Hg and having the formula:

having having (III);

perhydro- 1 ,1 ,3,4,4-pentamethylnaphthalene, the formula:

cg; iii) and havin the formula:

perhydro- 1 ,1 ,2,3,3,S-hexamethyl-3a,4-epoxy-7-indanone, having theformula:

(VII) l,2,3,4,5,6,7,8-octahydro-1,l,2,4,4,7-hexamethyl-8- naphthalenone,having the formula:

(VIII) l,2,3,4,5 ,6,7 ,8-octahydrol,1,3,4,4,6-hexamethyl-8-naphthalenone, having the formula:

perhydro- 1 1 ,2,4,4,7-hexamethyl-4a,5-epoxy-8-naphthalenone, having theformula:

perhydrol ,1 ,3,4,4,6-hexamethyl-4a,5-epoxy-8-naphthalenone, having theformula:

l,2,3,4,5 ,6,7,8-octahydro- 1,1 ,4,4-tetramethyl'-8-naphthalenone,having the formula:

('XII) perhydro- 1 1 ,4,4-tetramethyl-4a,5-epoxy-8-naphtha1enone, havingthe fonnula:

0 (XIII):

1,2,3 ,4,5 ,6,7,8-octahydro-1,1,2,4,4-pentamethy1-8- naphthalenone,having the formula:

perhydro-l ,1 ,2,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone, having theformula:

o (xv) 1,2,3,4,5,6,7,8-octahydrol l ,3,4,4-pentamethyl-8- naphthalenone,having the formula:

I (XVI):

perhydro-l ,1,3 ,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone, having theformula:

having the formula:

(xIx) The novel oxygenated compounds of this invention have variousfragrance notes. Thus, a mixture of compounds VI, VII, XVIII, and XIXadds a fruity, amber, woody fragrance to perfumes. A mixture of XIV, XV,XVI, and XVII has a fruity, wood, peach aroma flavor character. Amixture of compounds VIII, IX, X, and XI has a warm ambergris aroma.

The novel compounds disclosed herein can be prepared from thecorresponding indane or naphthalene hydrocarbons according to themethods herein disclosed. Thus, compound VT or VII can be prepared fromhexamethyl indane; compound VIII or X, fromhexamethyltetrahydronaphthalene; and similarly for other compounds.

One process for producing the novel compounds comprises treating thehydrocarbon having one aromatic ring with an alkali metal in thepresence of ammonia or an amine. Lithium is the preferred alkali metalbecause the reaction rategis higher and better completeness is obtained.The alkali metal is desirably added in a form having a high surface areaand pieces of the metallic ribbon have been used in certain preferredembodiments of the invention.

The amines used in conjunction with the alkali metal are desirablyprimary amines. The amines can 'be mono-amines having from two to fivecarbon atoms or diamines having from two to five carbon atoms. Ethylenediamine is an example of a primary amine preferred for use herein.

The amount of alkali metal used is in molar excess of the hydrocarbonbeing reduced, and amounts of from five to ten times the molar amount ofhydrocarbon are preferred. The amount of nitrogen compound, e.g.,diamines, used is generally sufficient to act as a vehicle for thereduction, so that is assists in moderating the reaction. Amounts ofamine from three to times the amount of hydrocarbon are desirably used.All parts, proportions, percentages, and ratios herein are by weightunless otherwise indicated.

When ammonia is utilized, the reaction is desirably carried out attemperatures of from about -50C to about 0C. Such temperatures obviatethe substantial superatmospheric pressures which would result fromhigher temperatures, but a satisfactory reaction rate is still obtained.

When the amine compounds are utilized, their relatively lower vaporpressures enable the reaction to be carried out at temperatures of 80Cto 150C to provide good completeness and to permit control of the coursethereof. Times on the order of two to eight hours are desirably used atthe preferred temperatures set forth herein.

Reduction of the aromatic ring, to provide monoenoic hydrocarbon, canalso be carried out by highpressure hydrogenation using a suitablecatalyst. Hydrogen pressures of from to 70 atmospheres are used attemperatures of 50C to 200C. The catalysts are desirably metalcatalysts, and nickel, particularly Raney nickel, and rhodium-on-carbonare preferred.

After hydrogenation is completed, the catalyst is removed by filtrationor other conventional techniques. The product is then purified ashereinafter disclosed.

The carbonyl oxygen-containing derivatives according to the presentinvention are prepared from monoenoic hydrocarbons obtained as taughtherein. The monoenoic hydrocarbons are treated with an oxidizing agent.Alkali metal dichromates are desirably used and sodium dichromate (Na CrO is a preferred agent.

The oxidation reaction is desirably carried out in the presence of anacidic medium, generally an alkanoic acid and preferably a lowercarboxylic acid having from two to four carbon atoms. A preferred acidicmedium is acetic acid.

The monoenoic hydrocarbon is generally utilized in molar excess of thedichromate to provide better reaction control. The molar quantity ofdichromate is desirably about percent to percent f the molar quantity ofthe monoenoic hydrocarbon. The carboxylic acid is generally used inamounts of from about four times to about ten times the quantity ofhydrocarbon.

The monoenoic or saturated hydrocarbons or the carbonyl derivativesproduced according to the above reaction schemes can be separated fromthe reaction medium, and any unreacted materials or unwanted by-productsremoved by conventional means including washing, distillation,crystallization, extraction, preparative chromatography and the like. Itis preferred fractionally to distill the washed reaction product under arelatively high vacuum so as to obtain a purified product or to isolatethe pure material.

The monoenoic hydrocarbons according to the present invention are usefulas intermediates in the preparation of fragrance materials, and arethemselves useful as olfactory agents. The carbonyl compounds of thisinvention are useful as fragrances. They can be used singly or incombination to contribute woody, ambergris, and/or fruity fragrances. Asolfactory agents the bicyclic derivatives of this invention can beformulated into or used a components of a perfume composition.

The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones, estersand frequently hydrocarbons which are admixed so that the combined odorsof the individual components produce a pleasant or desired fragrance.Such perfume compositions usually contain: (a) the main note or thebouquet or foundation-stone of the composition; (b) modifiers whichround-off and accompany the main note; (0) fixatives which includeodorous substances which lend a particular note to theperfume throughoutall stages of evaporation, and substances which retard evaporation; and(d) top-notes which are usually lowboiling fresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontribution by another ingredient in the composition.

The amount of the compounds of this invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as one percentof compounds or mixtures of compounds of this invention, or even less,can be used to impart desirable aromas to soaps, cosmetics, and otherproducts. The amount employed can range up to 15% or higher and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The bicyclic derivatives of this invention can be used alone or inperfume compositions as olfactory components in detergents and soaps;space deodorants; perfumes; colognes; bath preparations such as bathoil, bath salts; hair preparations such as lacquers, brilliantines,pomades, and shampoos; cosmetic preparations 7 such as creams,deodorants, hand lotions, sun screens; powders such as talcs, dustingpowders, face powder, and the like. When used as an olfactory componentof a perfumed article, as little as 0.011% of the novel bicyclics willsuffice to impart a good woody odor.

In addition, the perfume composition can contain a vehicle or carrierfor the other ingredients. The vehicle can be a liquid such as alcohol,glycol, or the like. The carrier can be an absorbent solid such as a gumor components for encapsulating the composition.

It will be appreciated that the bicyclic derivatives according to thisinvention can be used to enhance, modify, or supplement the fragranceproperties of natural or synthetic fragrance compositions. Thus, suchderivatives can be used in fragrance compositions for addition toperfume compositions or directly to products such as soap, detergents,cosmetics, and the like. The fragrance compositions so prepared do notentirely provide the olfactory properties to the finished perfume orother article, but they do furnish a substantial part of the overallfragrance impression.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I A l2-Iiter, three-necked reaction flask is charged with 505 g(2.5 mole) of l,l,2,3,3,5-hexamethylindane and 4700 cc ethylene diamine.The mixture is heated to 95C, and 140 g (20 mole) of lithium ribbon isadded slowly over four hours.

After the addition, the mixture is heated to reflux, so maintained forone hour, and cooled to 10C. Six liters of water is added slowly withcooling over two hours, while maintaining the temperature below 50C. Thereaction mass is stirred for two hours and then separated.

The aqueous layer is extracted thrice with threeliter portions oftoluene. The combined oil layers are washed consecutively with threeliters each of water, 5% aqueous hydrochloric acid, and water. Afterstripping off solvent, the residue is fractionated, using a 12-inchGoodloe column to give 369 g of 4,5,6,7-tetrahydro-l 1,2,3,3,5hexamethylindane (I).

EXAMPLE II A one-gallon stirred autoclave is charged with 900 g of 1, l,3 ,4,4,6-hexamethyl- 1 ,2,3 ,4-tetrahydronaphthalene, 900 ccisopropanol, and 45 g. of Raney nickel. Hydrogenation is conducted at1500 psi and 175-200C to an uptake of two moles of hydrogen. The oil isfreed of nickel catalyst by filtration and the solvent is stripped off.Gas-liquid chromatography (GLC) indicates the presence of approximately20% 1,l,3,4,4,6-hexamethyl-1,2,3,4,5,6,7,8,9-octahydronaphthalenone (II)and 20% of 1,1,3,4,4,6-hexamethylperhydronaphthalene (III), with theremainder being the starting material.

EXAMPLE III A 300 cc stirred autoclave is charged with 100 g (0.5 mole)of l l ,2,4,4-pentamethyll ,2,3 ,4-tetrahydronaphthalene and 5 g of 5%rhodium-on-carbon catalyst. Hydrogenation is conducted at 1000 psi and70C to an uptake of two moles of hydrogen.

8 The oil is freed of catalyst by filtration and GLC indicates thepresence of 30% of compound IV and 40% of the completely saturatedhydrocarbon V. The remainder is starting material.

EXAMPLE IV A 5-liter reaction flask is charged with 366 g (1.73 mole) of4,5,6,7-tetrahydro-l l ,2,3,3,5-hexamethylindane. A solution of 463 g(1.55 mole) of sodium dichromate in 1900 g of glacial acetic acid isadded dropwise over one hour while maintaining the reaction mass at C.After the addition is complete, stirring is continued at 75C for anotherseven hours.

After cooling to room temperature, 1.5 liters of water is added andafter stirring for 15 minutes, the layers are separated. The aqueousphase is extracted with one liter of toluene and the combined organiclayers are washed with one liter each of water, 5% aqueous sodiumhydroxide, and water.

The solvent is stripped off and the residue is fractionated to yield 141g (50% yield) of a mixture of compounds VI and VII of molecular weight220 and 236, respectively. The mixture also contains compounds XVIII andXIX.

EXAMPLE V The procedure of Example IV is repeated utilizing compound II,and a 15% yield of the mixture of compounds VIII, IX, X, and XI isobtained. The liquid shows IR (infrared) absorption at 1665 and 1590 cmattributed to conjugated carbonyl and absorption at 1710 cm attributedto EXAMPLE vi The procedure of Example IV is repeated utilizing 1,2,3,4,5,6,7,8-octahydro- 1., 1,4,4-tetramethylnaphthalene, and amixture of compounds XII and XIII is obtained in a 33% yield.

EXAMPLE VII The following mixture is prepared:

4'-ButyI-2',6-dimethyl-3 ,5 '-dinitroacetophenone Vanilla 75 Labdanumresin absolute 40 Patchouli oil 5 Cinnamic alcohol 10 Styrax clarifiedextra I0 Benzoin coeur 50 Mixture produced by the process of Example XII50 Lemon oil California Bergamot oil Italian Orange oil Florida 50 Nerolabsolute I 5 Petitgrain oil 75 Linalool synthetic 20 Linalyl acetatesynthetic 50 Geranium bourbon oil 10 Rosemary oil 5 Benzoin coeur l0Mixture produced by the process of Example IV 50 Addition of the mixtureproduced by the process of Example IV causes a fruity amber woodycharacter to be imparted to this mixture.

EXAMPLE IX The following mixture is prepared:

Z-Heptylcyclopentanone l Benzyl salicylate 20 Phenylethyl alcohol coeur100 4-(2,6,6-TrimethyLZ-cyclohexen- 1-yl)-3-methyl- 3-buten-2-one 25Petitgrain oil 30 p-Isopropyl-a-methylhydrocinnamaldehyde 25 n-Decanal lLauraldehyde 2 Methylnonyl acetaldehyde 0.5 Linalool synthetic 40Linalyl acetate 50 Mixture produced by the process of Example V 50 Theaddition of the mixture produced by the process of Example V imparts afruity woody peach note to the overall composition.

EXAMPLE X A 22-liter flask fitted with a mechanical stirrer,thermometer, condenser, and addition funnel is charged with 1400 g ofwater, and 4900 g of sulfuric acid is rapidly added while thetemperature is maintained at 30 to 40 with cooling. Then, 35 g of TritonX-100 octylphenoxypolyethoxyethanol surface active agent is added, andthis is followed by the dropwise addition of a mixture of 3500g (29.4moles) of alpha-methylsytrene and 1750 g (16.8 moles) of 2,3-dimethyl-2-hydroxybutane. The addition consumes 1-% hours and the temperature ismaintained at 30 to 35C.

The addition of the mixture is exothermic, and cooling is required tomaintain the temperature in the stated range. After addition iscomplete, the reaction mass is stirred for two hours at 30-35C; sixliters of water is added; and the mixture is then heated to 95C andstirred at that temperature for 30 minutes.

The reaction mass is left to stand for an additional 30 minutes afterstirring has been completed, and an emulsion forms. The mixture issaturated with sodium chloride and four additional liters of water areadded to cause separation of organic and aqueous layers. The aqueouslayer is extracted thrice with three liters of toluene, the extract iscombined with the organic phase, and the mass is washed with five litersof 5% aqueous sodium hydroxide and then with five liters of water. Thesolvent is stripped from the washed material, and the residue is vacuumdistilled commencing at 6 mm Hg to provide 1113 g of product, a 33%yield.

The 1 1 ,2,4,4-pentamethyll ,2,3 ,4-tetrahydronaphthalene so producedhas a boiling point of l38-142C at 1.5 mm Hg.

EXAMPLE XI A 12-liter flask equipped with stirrer, thermometer,condenser, and gas bubbler is charged with 490 g (2.2 moles) ofpentamethyltetrahydronaphthalene produced in Example X and 4125 g ofethylene diamine and heated to 95C, whereupon 12 3 '(17.6 moles) ofpieces of lithium ribbon are added during 2-% hours, while the tem eratre is fi aimaihea at 95 5C.. The rate of lithium addition is determinedby the evolution of gas. After all of the lithium is added the mass isheated to reflux and inaiiiiiiind under reflux for one 10 hour. Duringthis time, the color of the reaction mass changes from blue to a creamycolor.

The reaction mass is then cooled to 20C and six liters of water is addeddropwise with careful cooling to keep the highly exothermic reactionfrom raising the temperature above 60C. During the initial addition ofthe water, the mass becomes very viscous, but further addition of waterincreases the fluidity and makes the mass easier to stir. After thewater is added, the mass is stirred to dissolve all solids.

The stirring is discontinued to permit the formation of an aqueous layerand an organic layer and the aqueous layer is extracted once with twoliters of toluene. The toluene extract is added to the organic layer andthe mixture is washed successively with three liters of water, threeliters of 5% aqueous hydrochloric acid, and three liters of water. Thecrude is stripped of solvent, and vacuum distilled at 2.5 1.7 mm Hg.

A 68.5% yield ofl,l,3,4,4-pentamethyll,2,3,4,5,6,7,8-octahydronaphthalene (IV) isobtained with a boiling point of 100109C at 1.7 mm Hg.

EXAMPLE XII A 5-liter reaction flask equipped with a stirrer,thermometer, condenser, and addition funnel is charged with 309 g (1.5moles) of the product of Example XI and heated to 75C, and a solution of400 g sodium dichromate (1.35 moles) in 1650 cc of acetic acid is addeddropwise during a one-hour period. The reaction mass is then stirred foreight hours.

The mixture is cooled to 25C, 1.5 liters of water is added, the mixtureis stirred for 10 minutes, and the aqueous and organic phases are thenseparated. The aqueous layer is extracted once with 500 cc of toluene,and the toluene extract is combined with the organic layer. The organiclayer is then washed once successively with 500 cc of water, 500 cc of5% aqueous sodium hydroxide, and 500 cc of water. The crude oil isstripped free of solvent and vacuum distilled at 2.8 mm Hg.

The product obtained in a 25% yield is a mixture of XIV, XV, XVI, andXVII, boiling at l42149C at 2.8

mm Hg.

EXAMPLE XIII A l2-liter reaction flask equipped with a stirrer,thermometer, condenser, and addition funnel is charged with 667 g ofwater, and 2335 g (23.8 moles) of sulfuric acid is added as rapidly aspossible while maintaining the temperature at 30-40C. After 17 g ofTriton X-100 surface active agent is added, a mixture of 1850 g (14moles) p-methylalpha-methylstyrene and 816 g (8 moles) of2,3-dimethyl-Z-hydroxybutane is added dropwise at 30-35C with coolingduring one hour. The mixture is then stirred for 1% hours at 30-35C withslight cooliflg required to maintain the temperature. Five liters atwater is added, and the-mixture is heated Y6 C and maintained at thattemperature for 30 iitiiili tes'. The stirring is discontinued, and themixtiif is allowed to set for 30 minutes to separate into an faqii''oifi phase and an organic phase. The aqueous layer is withdrawn andextracted with two liters of 1 l The 1 1 ,2 ,4,4,7-hexamethyl- 1 ,2,3,4-tetrahydronaphthalene is obtained as a liquid boiling at l42l55C at2.5 mm Hg in a yield of 55%.

EXAMPLE XIV A l2-liter reaction flask equipped with stirrer,thermometer, and condenser is charged with 720 g (2 moles) of thetetrahydronaphthalene produced in Example XIII and 3750 cc of ethylenediamine. The flask contents are heated to 95C and 1 13 g (16.0 moles) ofmetallic lithium ribbon is added in the form of small pieces during a 1%hour period. The addition of lithium is exothermic and the flask iscooled to maintain the temperature at about 95C, the rate of additionbeing controlled by observation of the amount of gas evolved. The colorof the reaction mixture is blue so long as metallic lithium is present.Following the lithium addition, the reaction mass is refluxed for onehour.

The mass is then cooled to 10C and six liters of water is addeddropwise, with cooling required to maintain the exothermic wateraddition at a temperature below 40C. When about one liter of water isadded, the reaction mixture assumes a gelled consistency which liquifieson further addition of water. After the entire quantity of water isadded, the reaction mass is stirred for three hours to dissolve allsolid materials.

After the solids are dissolved, stirring is stopped and the reactionmass separates into aqueous and organic layers. The aqueous layer isextracted once with two liters of toluene, and the extract is combinedwith the organic layer. The combined extract and organic layer are thenwashed successively with three liters of water, three liters of 5%aqueous sodium hydroxide, and three liters of water. The solvent is thenstripped off and the remaining material is subjected to vacuumdistillation.

There is an 88% yield ofl,l,3,4,4,6-hexamethyll,2,3,4,5,6,7,8-octahydronaphthalene (II) mixedwith about of 1,1,3,4,4,6-hexamethylperhydronaphthalene. The mixture hasa boiling point of 116l24C at 2.0 mm Hg.

EXAMPLE XV A 5-liter reaction flask equipped with a stirrer,thermometer, condenser, and addition funnel is charged with 407 g (1.4moles) of 76% hexamethyloctahydronaphthalene produced in Example XIV.The flask is then heated to 75C and a mixture of 376 g (1.26 moles) ofsodium dichromate and 1540 g of acetic acid is added dropwise during onehour while the temperature is maintained at 75C. After addition of thesodium dichromate mixture is completed, the reaction mass is stirred for7 hours at 75C.

The mass is then cooled to 25C and 1.5 liters of water is added. Themixture is stirred for minutes and separated into two layers, and theaqueous phase is extracted once with one liter of toluene. The tolueneextract and organic layer are combined and washed successively with oneliter of water, one liter of 5% aqueous sodium hydroxide and one literof water. The solvent is stripped from the washed product and vacuumdistilled.

A liquid mixture of XIV, XV, XVI, and XVII, boiling at l 12-124C under 2mm Hg is obtained. The yield of the mixture products is about 30%. IRspectroscopy shows absorption at 1665 and 1590 cm attributed toconjugated carbonyl groups and absorption at 1710 cm attributed tounconjugated carbonyl groups.

EXAMPLE XVI A l2-liter reaction flask is equipped with stirrer,thermometer, condenser, and addition funnel is charged with 475 g ofwater and 1665 g of concentrated sulfuric acid is added with cooling tomaintain the temperature in the range of 3040C. Twelve grams of TritonX- is added, and this is followed by the dropwise addition of a mixtureof 1320 g (10 moles) of p-methyl-alpha-methylstyrene and 510 grams (5.8moles) of t-amyl alcohol, with the temperature being maintained at3035C. The addition takes one hour and the mixture is thereafter stirredat 3035C for 1- /2 hours. Thereafter, three liters of water is added,and the mixture is heated to 95C, and the temperature is maintained at35C for 30 mintues.

The mixture is allowed to set for 30 minutes and is then separated intoan aqueous and organic layer. The aqueous layer is extracted with twoliters of toluene and combined with the organic layer, and thecombination is washed successively with two liters of 5% aqueous sodiumhydroxide and two liters of water. The crude product is stripped toremove the solvent and vacuum distilled.

A 59% yield of liquid 1,l,2,3,3,5-hexamethylindane boiling at ll6l40C at2.5 mm Hg is obtained.

EXAMPLE XVII A l2-liter reaction flask equipped with stirrer,thermometer, condenser, and gas bubbler is charged with 505 g (2.5moles) of the indane produced in Example XVI and 4700 cc of ethylenediamine. The mixture is heated to 95C and g (20 moles) of lithium ribbonis added in the form of pieces during four hours. When all of thelithium has reacted, the color of the reaction mass changes from blue toyellow, and no additional gas is evolved. The rate of addition oflithium is controlled by adding further lithium when gas evolution fromthe previous addition has stopped. After lithium addition is complete,the mass is heated to reflux and maintained for one hour.

The mass is cooled to 10C and six liters of water is added dropwise withcooling to maintain the exothermic reaction below 50C. During wateraddition, the reaction mass gels, but upon further addition of water,the solids dissolve. The water addition takes about two hours, and thenthe mass is stirred for an additional two hours and permitted toseparate into two phases.

The aqueous phase is extracted with three liters of toluene and combinedwith the organic phase and the combination is washed successively withthree liters of water, three liters of 5% aqueous hydrochloric acid andthree liters of water. The solvent is stripped off and the product isvacuum distilled.

1, l ,2,3 ,3,5-Hexamethyl-4,5,6,7-tetrahydroindane (I) is obtained in a75.8% yield as a liquid boiling at 9295C at 3 mm Hg.

EXAMPLE XIII A 5-liter reaction flask equipped with stirrer,thermometer, condenser, and addition funnel is charged with 366 g (1.73moles) of 97.2% pure pentamethylindane produced in Example XVII. Theflask is heated to 75C and a mixture of 463 g (1.55 moles) of sodiumdichromate and 1900 g of acetic acid is added dropwise during one hour.After the addition is complete, the mass is stirred for seven additionalhours at 75C.

The mass is cooled to 25C, 1.5 liters of water is added, and the mixtureis stirred for 15 minutes. The aqueous and organic phasesare separatedand the aqueous phase is extracted with a liter of toluene. The tolueneextract is combined with the organic layer, and the combination iswashed successively with a liter of water, a liter of 5% aqueous sodiumhydroxide, and a liter of water. The solvent is stripped from themixture, and the mixture is then vacuum distilled.

A mixture of VI, VII, XVIII, XIX is obtained as a liquid boiling at 1 ll16C at 2 mm Hg in a yield of 48%. Infrared (IR) spectroscopy showsabsorption at 1665 and 1625 cm attributable to conjugated carbonylgroups and absorption at 1710 cm attributable to unconjugated carbonylgroups.

EXAMPLE XIX A high-pressure autoclave is charged with 900 g 1,1,3,4,4,6-hexamethyl-1 ,2 ,3 ,4-tetrahydronaphthalene, 900 cc ofisopropanol, and 45 g of Raney nickel catalyst. The hydrogenationreaction is started at 50C and 300 psig (pounds per square inch, gauge)pressure, and over a four-hour time the temperature is raised to 200Cand the pressure to 1200 psig.

After the foregoing hydrogenation is completed, the catalyst is filteredoff and the solvent is stripped from the reaction mixture. Massspectroscopic analysis of the product shows it contains 20%1,1,3,4,4,6-hexamethyll ,2,3,4,5,6,7,8-octahydronaphthalene (II) and 20%1 ,2,3 ,4,5 ,6-hexamethylperhydronaphthalene.

EXAMPLE XX A high-pressure autoclave is charged with 200 cc of l ,1 ,3,4,4,6-hexamethyl- 1 ,2 ,3,4-tetrahydronaphthalene and 5 g of 5%rhodium-on-carbon catalyst. The hydrogenation is commenced at 32C and280 psig, and the temperature and pressure are, respectively, raised to175C and 1500 psig during 2.5 hours. An additional 5 g of the aforesaidcatalyst is then added, and the hydrogenation is continued at l00155Cand 1500 psig for another hour.

After the foregoing hydrogenation is completed the catalyst is filteredoff. Gas-liquid chromatography (GLC) shows that the 86 g of product isobtained is 1,1 ,3,4,4,6-hexamethyl-l ,2 ,3,4,5,6,7,8-octahydronaphthalene.

EXAMPLE XXI A high-pressure autoclave is charged with 101 g (0.5 moles)of 1,1,2,4,4-pentamethyl-1 ,2,3,4-tetrahydronaphthalene and 5 g of 5%rhodium-on-carbon catalyst. The hydrogenation is begun at 25C and 1000psig pressure, and after about an hour the temperature is graduallyraised to 75C, and the reaction is completed in about 2 hours and 20minutes.

After the material is removed from the autoclave the catalyst isseparated by filtration. GLC analysis shows that 30 percent of thematerial is 1,l,2,4,4-pentamethyl-l,2,3,4,5,6,7,8-octahydronaphthaleneand that 40 percent is 1,1,2,4,4-pentamethyl-1,2,3 ,4,5,6-hexahydronaphthalene. Mass spectroscopy confirms these results.

What is claimed is:

l. A perfume composition containing as an essential fragrance ingredientl ,2,3,4,5 ,6,7,8-octahydrol,l,2,4,4-pentamethyl-8-naphthalenone havingthe formula and an auxiliary perfume adjuvant selected from the groupconsisting of perfume modifiers, fixatives and top-notes.

2. A composition as defined in claim 1 which additionally comprises1,2,3 ,4,5,6,7,8-octahydro-1 ,l,3,4,4- pentamethyl-8-naphthalenone;perhydrol ,1 ,2,4,4- pentamethyl-4a,5-epoxy-8-naphthalenone; andperhydro- 1 ,1,3 ,4,4-pentamethyl-4a,S-epoxy-S-naphthalenone.

3. A process for altering the fragrance properties of a perfumedcomposition which comprises adding at least about 0.011 per cent byweight based on the weight of said composition of1,2,3,4,5,6,7,8-octahydrol, l ,2,4,4-pentamethyl-8-naphthalenonethereto.

4. A process as defined in claim 3, wherein said compositionadditionally contains 1,2,3,4,5,6,7,8-octahydro- 1 ,1 ,3 ,4,4-pentamethyl-8-naphthalenone; perhydro-l 1 ,2,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone; and perhydrol ,l,3,4,4-pentamethyl-4a,5-epoxy- S-naphth alenone.

UNITED STATES PATENT OFFICE CERTIFICATE @F CORREC'HN PATENT NO. 3,927,083

DATED 3 December 16, 1975 JOHN B. HALL LEKHU KEWALRAM LALA INVENTOR(S)MUUS G. J. BEETS, and WILLIAM I. TAYLOR It is certified that errorappears in the ab0ve-identified patent and that said Letters Patent arehereby corrected as shown below:

Col. 1, line 36, "sued" should read -used Col. 8, line 33, complete thesentence and insert after "to" -unconjugated carbonyl-- Col. 8, ExampleVII, insert "-tafter "4' Col. 9 line 32, at the end of the line"methylsy" should read methylsty- Signed and Sealed this Twenty-seventhDay Of July 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN 4119811718 ff Commissioner of Parents andTrademarks

1. A PERFUME COMPOSITION CONTAINING AS AN ESSENTIAL FRAGRANCE INGREDIENT 1,2,3,4,5,6,7,8-OCTAHYDRO-1,1,2,4,4-PENTAMETHYL-8-NAPTHALENONE HAVING THE FORMULA
 2. A composition as defined in claim 1 which additionally comprises 1,2,3,4,5,6,7,8-octahydro-1,1,3,4,4-pentamethyl-8-naphthalenone; perhydro-1,1,2,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone; and perhydro-1,1,3,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone.
 3. A process for altering the fragrance properties of a perfumed composition which comprises adding at least about 0.011 per cent by weight based on the weight of said composition of 1,2,3,4,5,6, 7,8-octahydro-1,1,2,4,4-pentamethyl-8-naphthalenone thereto.
 4. A process as defined in claim 3, wherein said composition additionally contains 1,2,3,4,5,6,7,8-octahydro-1,1,3,4,4-pentamethyl-8-naphthalenone; perhydro-1,1,2,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone; and perhydro-1,1,3,4,4-pentamethyl-4a,5-epoxy-8-naphthalenone. 